Crystal‐Phase‐Engineered PdCu Electrocatalyst for Enhanced Ammonia Synthesis

Abstract

Crystal phase engineering is a powerful strategy for regulating the performance of electrocatalysts towards many electrocatalytic reactions, while its impact on the nitrogen electroreduction has been largely unexplored. Herein, we demonstrate that structurally ordered body‐centered cubic (BCC) PdCu nanoparticles can be adopted as active, selective, and stable electrocatalysts for ammonia synthesis. Specifically, the BCC PdCu exhibits excellent activity with a high NH3 yield of 35.7 μg h−1 mg−1cat, Faradaic efficiency of 11.5 %, and high selectivity (no N2H4 is detected) at −0.1 V versus reversible hydrogen electrode, outperforming its counterpart, face‐centered cubic (FCC) PdCu, and most reported nitrogen reduction reaction (NRR) electrocatalysts. It also exhibits durable stability for consecutive electrolysis for five cycles. Density functional theory calculation reveals that strong orbital interactions between Pd and neighboring Cu sites in BCC PdCu obtained by structure engineering induces an evident correlation effect for boosting up the Pd 4d electronic activities for efficient NRR catalysis. Our findings open up a new avenue for designing active and stable electrocatalysts towards NRR.

Electrochemical ammonia synthesis: Mechanistic understanding and catalyst design

“…96 Additionally, effective d-d coupling between two metal sites may occur, which can bridge the electron transfer Coulomb gap toward rapid NRR. 172 Single-atom sites display distinct catalytic activities due to low-coordination environment of the metal center, quantum size effects, and metal-support interactions. Review stabilize *N 2 H, and destabilize *NH 2 species.…”

Lithium-mediated electrochemical nitrogen reduction: Mechanistic insights to enhance performance

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Boosting Electrocatalytic Ammonia Production through Mimicking “π Back-Donation”

“…[2][3][4][5][6][7] Attributed to the availability of d-orbital electrons, advances in the chemistry of electrocatalytic N 2 RR have indicated transition-metal-based catalysts can produce NH 3 through the ''p back-donation'' process to alleviate the kinetic barrier of N 2 activation. [8][9][10][11][12][13][14] Nevertheless, because of the adverse hydrogen evolution reaction (HER), it remains a grand challenge in improving the selectivity (faradic efficiency [FE]). 15,16 Alternatively, p-block elements might serve as promising electrocatalysts for N 2 RR owing to their unique electronic structure and poor HER activity.…”